In this communication, we investigated the effects of LiNiVO 4 thin film electrodes composition, thickness, electrolytes, cycling temperature, crystallization of films, and substrates on the kinetics during lithium insertion/de-insertion behaviour, which were studied in detail by cyclic voltammetry. The stoichiometric and non-stoichiometric thin films were formed by using rf-sputtering by varying the partial pressure of oxygen, and the host films were characterized by a variety of methods like Nuclear techniques and surface science analytical methods. The galvanostatic studies give the lithium insertion amounts and the best electrochemical performance of 1300mAh/g capacity has been obtained from the stoichiometric film deposited on a stainless steel substrate during the first discharge cycle. The lithium diffusion coefficients of the film during the first discharge–charge cycle were measured by using galvanostatic intermediate titration method. Overall, the voltammetric behaviours of LiNiVO 4 thin film electrodes are highly sensitive to the composition, thickness, cycling temperature, scan rate, substrates and crystal structure, and the above observed behaviours are discussed.